Premium
Ultimate Control over Hydrogen Bond Formation and Reaction Rates for Scalable Synthesis of Highly Crystalline vdW MOF Nanosheets with Large Aspect Ratio
Author(s) -
Shen Yuxia,
Shan Bohan,
Cai Hui,
Qin Ying,
Agarwal Ashutosh,
Trivedi Dipesh B.,
Chen Bin,
Liu Lei,
Zhuang Houlong,
Mu Bin,
Tongay Sefaattin
Publication year - 2018
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.201802497
Subject(s) - crystallinity , van der waals force , materials science , hydrogen bond , raman spectroscopy , nanotechnology , chemical engineering , molecule , chemical physics , composite material , organic chemistry , chemistry , physics , optics , engineering
Abstract Large‐scale synthesis of van der Waals (vdW) metal–organic framework (MOF) nanosheets with controlled crystallinity and interlayer coupling strength is one of the bottlenecks in 2D materials that has limited its successful transition to large‐scale applications. Here, scalable synthesis of mBDC (m = Zn and Cu) 2D MOFs at large scales through a biphase method is demonstrated. The results show replacing water molecules with pyridine eliminates hydrogen bond formation at metal cluster sites. This prohibits tight coupling across adjacent MOF layers and sustains controllable 2D vdW MOF growth. It is further shown that control over the growth speed, crystallinity, and thickness can be achieved by addition of a controlled amount of triethylamine and formic acid to achieve highly crystalline vdW MOF nanosheets with extraordinarily high aspect ratio. The described synthesis route can easily be scaled up for large‐scale production either by deposition onto desired substrates or in crystalline layered powder form. Owing to its large lateral size, vdW nature, and high crystallinity, it is possible to perform atomic force microscopy, Kelvin probe force microscopy, and Raman measurements on the 2D MOFs. The results not only establish their vibrational properties and layer‐dependent responses but also show striking differences from other 2D inorganic materials.